WO2013089187A1 - Film réfléchissant dans l'infrarouge - Google Patents

Film réfléchissant dans l'infrarouge Download PDF

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Publication number
WO2013089187A1
WO2013089187A1 PCT/JP2012/082351 JP2012082351W WO2013089187A1 WO 2013089187 A1 WO2013089187 A1 WO 2013089187A1 JP 2012082351 W JP2012082351 W JP 2012082351W WO 2013089187 A1 WO2013089187 A1 WO 2013089187A1
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Prior art keywords
protective layer
layer
infrared
reflective film
infrared reflective
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PCT/JP2012/082351
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English (en)
Japanese (ja)
Inventor
元子 河▲崎▼
潤一 藤澤
聖彦 渡邊
大森　裕
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日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to EP12856615.5A priority Critical patent/EP2792484A1/fr
Priority to US14/365,258 priority patent/US20140327959A1/en
Priority to CN201280062240.3A priority patent/CN103987522A/zh
Publication of WO2013089187A1 publication Critical patent/WO2013089187A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • G02B5/0816—Multilayer mirrors, i.e. having two or more reflecting layers
    • G02B5/085—Multilayer mirrors, i.e. having two or more reflecting layers at least one of the reflecting layers comprising metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/006—Transparent parts other than made from inorganic glass, e.g. polycarbonate glazings

Definitions

  • the present invention relates to an infrared reflective film having high transparency in the visible light region and high reflectivity in the infrared light region.
  • the infrared reflective film is mainly used for suppressing the thermal effect of the emitted sunlight.
  • an infrared reflecting film is pasted on a window glass of a building or an automobile, so that infrared rays (particularly near infrared rays) that enter the room through the window glass are shielded and the temperature rise in the room is thereby suppressed. It is possible to save energy by suppressing power consumption.
  • Patent Document 1 discloses using polyacrylonitrile (PAN) as a material for the protective layer.
  • PAN polyacrylonitrile
  • Polymers such as polyacrylonitrile have a low infrared absorptivity and can shield far-infrared rays emitted from the room through the translucent member. Energy saving can also be achieved by the heat insulation effect.
  • the protective layer is prepared by first dissolving the polymer in a solvent to prepare a solution, and then applying this solution on the infrared reflective layer. Is dried (the solvent is volatilized).
  • this kind of infrared reflective film is stuck on a window glass of a building or an automobile so that the protective layer is on the front side. Therefore, the surface of the protective layer is always subjected to various stresses from the outside. Therefore, if the protective layer does not have sufficient strength (hardness), the protective layer may be pushed in due to external stress and deformed greatly, resulting in poor appearance. Further, when the infrared reflective layer is exposed due to deformation of the protective layer, the infrared reflective layer is easily damaged. As a result, there arises a problem that the infrared reflection characteristics are impaired and the infrared reflection film does not function sufficiently.
  • the present invention has been made in view of such circumstances, and an object thereof is to provide an infrared reflective film in which deformation of the protective layer due to pressing is suppressed.
  • the protective layer is a layer containing a polymer containing at least any two or more repeating units among the repeating units A, B and C represented by the following chemical formula I:
  • the indentation hardness of the protective layer is 1.2 MPa or more.
  • the protective layer may have a crosslinked structure of the polymer.
  • the crosslinked structure can be formed by irradiating the protective layer with an electron beam.
  • the vertical emissivity of the surface on the protective layer side can be 0.20 or less.
  • a water-based urethane adhesive layer may be further provided between the reflective layer and the protective layer.
  • the schematic diagram for demonstrating the laminated structure of the infrared reflective film which concerns on one Embodiment of this invention is shown. It is a schematic diagram for demonstrating the contact projected area measured by an indentation test, Comprising: The state which pushed the indenter into the protective layer is shown. It is a schematic diagram for explaining the contact projected area measured by the indentation test, and shows the I arrow view of FIG. 2A in which the measurement range of the contact projected area is hatched.
  • the infrared reflective film which concerns on this embodiment is an infrared reflective film which has a heat insulation characteristic (reflective characteristic of far infrared rays) in addition to the thermal insulation characteristic (reflective characteristic of near infrared rays) which the conventional infrared reflective film has.
  • a reflective layer 2 and a protective layer 3 are laminated in that order on one surface 1a of a substrate 1, and an adhesive layer 4 is provided on the other surface 1b. It has a layer structure.
  • a polyester film is used as the substrate 1.
  • a film made of polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexylene methylene terephthalate, or a mixed resin in which two or more of these are combined is used.
  • a polyethylene terephthalate (PET) film is preferable from the viewpoint of performance, and a biaxially stretched polyethylene terephthalate (PET) film is particularly preferable.
  • the reflective layer 2 is a vapor deposition layer formed by vapor deposition on the surface (one surface) 1a of the substrate 1.
  • Examples of the method for forming the vapor deposition layer include physical vapor deposition (PVD) such as sputtering, vacuum vapor deposition, and ion plating.
  • PVD physical vapor deposition
  • the reflective layer 2 is formed on the substrate 1 by heating and evaporating the vapor deposition material by a method such as resistance heating, electron beam heating, laser beam heating, or arc discharge in vacuum.
  • a vacuum containing an inert gas such as argon cations such as Ar + accelerated by glow discharge are bombarded on the target (vapor deposition material) to vaporize the vapor deposition material.
  • the reflective layer 2 is formed on the substrate 1.
  • Ion plating is a vapor deposition method that combines vacuum vapor deposition and sputtering. In this method, the evaporation layer released by heating is ionized and accelerated in an electric field in vacuum, and is deposited on the substrate 1 in a high energy state, whereby the reflective layer 2 is formed.
  • the reflective layer 2 has a multi-layer structure in which a translucent metal layer 2a is sandwiched between a pair of metal oxide layers 2b and 2c. Surface) 1a, a metal oxide layer 2b is deposited, then a semitransparent metal layer 2a is deposited on the metal oxide layer 2b, and finally a metal oxide layer 2c is deposited on the semitransparent metal layer 2a. Formed.
  • the translucent metal layer 2a includes, for example, aluminum (Al), silver (Ag), silver alloy (MgAg, Ag—Pd—Cu alloy (APC), AgCu, AgAuCu, AgPd, AgAu, etc.), aluminum alloy (AlLi, AlCa) , AlMg, etc.), or a metal material in which two or more of these are combined.
  • the metal oxide layers 2b and 2c are for imparting transparency to the reflective layer 2 and preventing deterioration of the translucent metal layer 2a.
  • ITO indium tin oxide
  • IT indium titanium oxide
  • An oxide such as indium zinc oxide (IZO), gallium zinc oxide (GZO), aluminum zinc oxide (AZO), or indium gallium oxide (IGO) is used.
  • the protective layer 3 is a layer containing a polymer containing at least any two or more repeating units among the repeating units A, B and C of the following chemical formula I.
  • R1 in Chemical Formula I H or a methyl group can be used.
  • R2 to R5 in Chemical Formula I H and an alkyl group or alkenyl group having 1 to 4 carbon atoms can be used.
  • hydrogenated nitrile rubber (HNBR) is composed of repeating units A, B and C, and H is used as R1 to R5.
  • Examples of monomer components for obtaining these polymers include acrylonitrile (repeating unit D) and derivatives thereof as shown in Chemical Formula II, alkyl having 4 carbon atoms (repeating unit E) and derivatives thereof, and butadiene ( And a copolymer of the repeating unit F1 or F2) and derivatives thereof.
  • R6 represents H or a methyl group
  • R7 to R18 represent H or an alkyl group having 1 to 4 carbon atoms.
  • Each of F1 and F2 represents a repeating unit in which butadiene is polymerized, and F1 is a main repeating unit.
  • nitrile rubber or nitrile rubber which is a copolymer of acrylonitrile of formula II (repeating unit D) and derivatives thereof, 1,3-butadiene (repeating unit F1) and derivatives thereof.
  • Hydrogenated nitrile rubber in which part or all of the double bond is hydrogenated may be used.
  • the butadiene on the left side is bonded to the side to which the cyano group (—CN) of acrylonitrile is bonded, and the butadiene on the right side is formed to the side to which the cyano group (—CN) of acrylonitrile is not bonded.
  • one repeating unit A, one repeating unit B, and two repeating units C are included.
  • the repeating unit A includes a carbon atom in which the carbon atom on the right side of the butadiene on the left side is bonded to the cyano group (—CN) of acrylonitrile, and the repeating unit B is bonded to the cyano group (—CN) of acrylonitrile.
  • the indentation hardness of the protective layer 3 is 1.2 MPa or more.
  • the indentation hardness can be measured by an indentation test using a micro hardness tester, which is a kind of hardness test. That is, the indentation hardness is a region where the indenter C is in contact with the protective layer 2 in a state where the triangular pyramid-shaped indenter C is pushed into the protective layer 3 to a predetermined indentation depth D as shown in FIGS. 2A and 2B.
  • the area (projection contact area) A of the projection area PA as viewed from the indentation direction of the indenter C and the indentation load P of the indenter C are measured, and the projection contact area obtained by the measurement (obtained by observation in situ) It is calculated based on the following formula 1 from the indentation load P of A and the indenter C.
  • H P / A Formula 1 (H: indentation hardness, P: load, A: projected contact area)
  • the projected contact area As a method of measuring the projected contact area, it is possible to measure by the method disclosed in JP-A-2005-195357. Specifically, a transparent one is used for the indenter C, and a contact area between the protective layer 3 and the indenter C that is visually recognized through the indenter C from above the indenter C (above the indenter C is pushed in). By capturing an image with an image sensor such as a CCD camera, the area (contact projection area) A of the projection area PA can be measured.
  • the material of the indenter C may be any material as long as it has a high hardness and is transparent enough to measure the projected contact area A. Diamond, single crystal alumina oxide (sapphire, ruby), or translucent alumina polycrystal Meets these requirements.
  • a measuring apparatus for realizing the above measuring method there is a trade name “observation type micromaterial evaluation system, microindent scope MIS-2000 (manufactured by Sankosha Co., Ltd.)”.
  • the protective layer 3 is prepared by dissolving the above-described polymer in a solvent (along with a crosslinking agent as necessary) to prepare a solution, and applying this solution on the reflective layer 2. It is formed by the procedure of drying (volatilizing the solvent).
  • the solvent is a solvent in which the above-described polymer is soluble.
  • a solvent such as methyl ethyl ketone (MEK) or methylene chloride (dichloromethane) is used.
  • MEK methyl ethyl ketone
  • methylene chloride dimethyl ketone
  • Methyl ethyl ketone and methylene chloride are low boiling point solvents (methyl ethyl ketone is 79.5 ° C., methylene chloride is 40 ° C.). Therefore, when these solvents are used, the solvent can be volatilized at a low drying temperature, so that the substrate 1 (or the reflective layer 2) is not damaged by heat.
  • the lower limit of the thickness of the protective layer 3 is 1 ⁇ m or more. Preferably, it is 3 ⁇ m or more. Moreover, as an upper limit, it is 20 micrometers or less. Preferably, it is 15 ⁇ m or less. More preferably, it is 10 ⁇ m or less.
  • the thickness of the protective layer 3 is small, the infrared reflection characteristics are enhanced, but the scratch resistance is impaired, and the function as the protective layer 3 cannot be sufficiently exhibited. If the thickness of the protective layer 3 is large, the heat insulating property of the infrared reflective film is deteriorated. When the thickness of the protective layer 3 is within the above range, the protective layer 3 that can absorb the infrared rays and can appropriately protect the reflective layer 2 is obtained.
  • the spectral reflectance ⁇ n is measured in the wavelength range of 5 to 50 ⁇ m of room temperature thermal radiation.
  • the wavelength region of 5 to 50 ⁇ m is the far infrared region, and the vertical emissivity decreases as the reflectance in the far infrared wavelength region increases.
  • the protective layer 3 preferably has a crosslinked structure of polymers.
  • the solvent resistance of the protective layer 3 is improved, so that the protective layer 3 is prevented from eluting even when a solvent soluble in the polymer contacts the protective layer 3. can do.
  • the cumulative irradiation dose of the electron beam is 50 kGy or more as a lower limit value. Preferably, it is 100 kGy or more. More preferably, it is 200 kGy or more. Moreover, as an upper limit, it is 1000 kGy or less. Preferably, it is 600 kGy or less. More preferably, it is 400 kGy or less.
  • the cumulative irradiation dose refers to the irradiation dose when the electron beam is irradiated once, and the total irradiation dose when the electron beam is irradiated a plurality of times.
  • the single irradiation dose of the electron beam is preferably 300 kGy or less. If the integrated irradiation dose of the electron beam is within the above range, sufficient crosslinking between the polymers can be obtained. Moreover, if the integrated irradiation dose of the electron beam is within the above range, yellowing of the polymer and the substrate 1 generated by the electron beam irradiation can be minimized, and an infrared reflective film with less coloring can be obtained. Can do.
  • These electron beam irradiation conditions are irradiation conditions at an acceleration voltage of 150 kV.
  • a crosslinking agent such as a polyfunctional monomer such as a radical polymerization type monomer when the polymer is dissolved in the solvent or after the polymer is dissolved in the solvent.
  • a polyfunctional monomer such as a radical polymerization type monomer
  • radical polymerization monomers of (meth) acrylate monomers are preferred.
  • the accumulated irradiation dose of the electron beam can be completed with a low irradiation dose. Moreover, yellowing of the polymer and the substrate 1 can be further suppressed by reducing the cumulative irradiation dose of the electron beam, and productivity can be improved.
  • the amount of the additive added increases, the vertical emissivity of the surface of the infrared reflecting film on the protective layer 3 side (based on the reflective layer 2) deteriorates.
  • the amount of the additive added is preferably 1 to 35% by weight with respect to the polymer. More preferably, it is 2 to 25% by weight based on the polymer.
  • the infrared reflective film according to the present embodiment includes a water-based urethane adhesive layer (not shown) between the reflective layer 2 and the protective layer 3.
  • the aqueous urethane adhesive layer can be obtained, for example, by applying an aqueous polyurethane resin composition containing a polyurethane resin aqueous dispersion and a polyisocyanate aqueous dispersion on the reflective layer and then drying it. Since the water-dispersed urethane adhesive does not contain a solvent, it is preferable in that the environmental load can be reduced.
  • the polyurethane resin aqueous dispersion is obtained by crosslinking polyester polyol or organic polyisocyanate with polyamine. Furthermore, the polyurethane resin aqueous dispersion further comprises a compound having a polyol and / or an alicyclic polyol having an aromatic ring having a number average molecular weight of less than 500, or a compound having an anionic hydrophilic group such as a carboxyl group in the molecule. It may be included and may be cross-linked.
  • Examples of the compound having an aromatic ring having a number average molecular weight of less than 500 and / or an alicyclic polyol include bisphenol A, bisphenol F, bisphenol S, 1,4-cyclohexanediol, 1,4-cyclohexane. And dimethanol.
  • examples of the compound having such an anionic hydrophilic group include dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolvaleric acid and the like.
  • Polyamine is a compound having two or more amino groups in the molecule, and examples thereof include ethylenediamine and propylenediamine.
  • aqueous dispersion of polyisocyanate examples include, for example, an isocyanurate modified product of hexamethylenediamine diisocyanate (trade name “Aquanate 100” manufactured by Nippon Polyurethane Industry Co., Ltd.), an adduct modified product of hexamethylene diisocyanate (trade name manufactured by Asahi Kasei Chemicals Corporation). "Duranate WB40-80D").
  • the aqueous polyurethane resin composition is preferably blended so that the solid content of the polyisocyanate aqueous dispersion is 10 to 80% by weight relative to 100% by weight of the solid content of the polyurethane resin aqueous dispersion.
  • a cross-linking agent may be included.
  • crosslinking agent examples include organic amino groups, oxazoline groups, epoxy groups, carbodiimide groups, and the like. These compounds are groups that can react satisfactorily when a carboxyl group is contained in the polyurethane resin aqueous dispersion or polyisocyanate aqueous dispersion, and particularly preferred is a case having an oxazoline group.
  • a crosslinking agent having an oxazoline group is preferable in terms of good workability because the pot life at room temperature of the aqueous polyurethane resin composition at the time of use is long and the crosslinking reaction proceeds by heating.
  • aqueous polyurethane resin composition examples include “Superflex” series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., such as Superflex 210 and Superflex 170.
  • the thickness of the adhesive layer is 10 nm or more as a lower limit. Preferably, it is 50 nm or more. Moreover, as an upper limit, it is 600 nm or less. Preferably, it is 300 nm or less. If the thickness of the adhesive layer is less than 10 nm, there is a possibility that sufficient adhesive force cannot be imparted, and if it exceeds 600 nm, the heat insulating function may be lowered.
  • the drying temperature is 60 ° C. or higher, preferably 100 ° C. or higher.
  • a urethane-based adhesive layer is formed between the reflective layer 2 and the protective layer 3, but the present invention is not limited to this, and the reflective layer 2 and the protective layer 3 A urethane-based adhesive layer may not be formed therebetween.
  • the thickness of the layer structure on the reflective layer 2, that is, the thickness of the protective layer 3 is reduced to protect (based on the reflective layer 2).
  • the vertical emissivity of the surface on the layer 3 side is small.
  • the protective layer 3 is made of nitrile rubber, hydrogenated nitrile rubber, fully hydrogenated nitrile rubber, or the like, which hardly absorbs far-infrared rays and is easily transmitted, the vertical emissivity is also reduced. Accordingly, far infrared rays are not easily absorbed by the protective layer 3 even if they are incident on the protective layer 3, reach the reflective layer 2, and as a result, are easily reflected by the reflective layer 2.
  • the infrared reflective film according to the present embodiment by sticking the infrared reflective film according to the present embodiment to a light transmissive member such as a window glass from the indoor side, it is possible to shield far infrared rays emitted from the room through the light transmissive member to the outside. In this way, a heat insulation effect can be expected in winter and at night when the indoor temperature decreases.
  • the vertical emissivity of the surface on the protective layer 3 side is set to 0.20 or less for the purpose. More preferably, the vertical emissivity is 0.15 or less.
  • the translucency of a translucent member is not inhibited by making visible light transmittance (refer JIS A5759) high.
  • the visible light transmittance is set to 50% or more for the purpose.
  • the infrared reflective film according to the present embodiment to a light transmissive member such as a window glass from the indoor side, the near infrared light incident on the room through the light transmissive member such as the window glass is shielded.
  • a heat shielding effect in summer can be expected.
  • the solar radiation transmittance (see JIS A5759) when light is incident from the surface of the substrate 1 (based on the reflective layer 2) is 60% or less.
  • the infrared reflective film which concerns on this embodiment, since the indentation hardness of the protective layer 3 is 1.2 Mpa or more as mentioned above, the deformation amount of the protective layer 3 by indentation becomes small, As a result, protection Layer 3 is less likely to be partially or wholly destroyed. Therefore, it is possible to prevent a situation in which the reflective layer 2 having low scratch resistance is exposed due to destruction of the protective layer 3 and the reflective layer 2 is damaged. Moreover, this can prevent the infrared reflection characteristics from being impaired and the infrared reflection film from sufficiently functioning.
  • the protective layer 3 since the polymers in the protective layer 3 are cross-linked, the protective layer 3 has improved solvent resistance in addition to suppressing deformation due to indentation. Thereby, even if the solvent which melt
  • the present inventors produced an infrared reflective film according to the present embodiment (Examples 1 to 7), and also produced a comparative infrared reflective film (Comparative Examples 1 and 2).
  • An indentation test was performed with a micro hardness tester, and their vertical emissivity was measured.
  • Example 1 to 7 and Comparative Examples 1 and 2 the production method is as follows.
  • a polyethylene terephthalate film (trade name “Diafoil T602E50” manufactured by Mitsubishi Plastics, Inc.) having a thickness of 50 ⁇ m was used as the substrate 1.
  • a reflective layer 2 was formed on one surface 1a of the substrate 1 by DC magnetron sputtering. Specifically, using a DC magnetron sputtering method, a metal oxide layer 2b made of indium tin oxide is formed with a thickness of 35 nm on one surface 1a of the substrate 1, and a translucent made of an Ag—Pd—Cu alloy is formed thereon.
  • the metal layer 2a was formed with a thickness of 18 nm, and the metal oxide layer 2c made of indium tin oxide was formed thereon with a thickness of 35 nm.
  • a protective layer 3 was formed on the reflective layer 2 by a coating method. In addition, the detailed formation conditions of the protective layer 3 are explained in full detail in description of an Example and a comparative example, respectively.
  • the laminate was fixed on the stage so that the protective layer 3 was on the surface side, and the indenter C was pushed into the protective layer 3 until the predetermined depth D was reached with reference to the surface of the protective layer 3. .
  • the indentation load P and the projected contact area A with respect to the indenter C in that state were measured, and the indentation hardness was calculated from the above equation 1.
  • the indenter C a Barkovic diamond indenter was used as the indenter C.
  • the indentation depth D of the indenter C relative to the surface of the protective layer 3 was 3 ⁇ m, and the indentation speed of the indenter C was 0.1 ⁇ m / second.
  • the measuring method of vertical emissivity is as follows. Using a Fourier transform infrared spectroscopic (FT-IR) device (Varian) equipped with a variable angle reflection accessory, the regular reflectance of infrared light having a wavelength of 5 to 25 microns was measured, and JIS R 3106- It calculated
  • FT-IR Fourier transform infrared spectroscopic
  • Example 1 Fully hydrogenated nitrile rubber (NBM: LANXESS, trade name “Terban 5005” [k: 33.3, l: 66.7, m: 0, R1 to R3: H]) 10% by weight and methyl ethyl ketone (Wako Pure Chemical Industries, Ltd.) 90% by weight) (mixed by Kogyo Co., Ltd.) was mixed and dissolved by stirring at a temperature of 80 ° C. for 5 hours. The hydrogenated nitrile rubber was dissolved in a solvent of methyl ethyl ketone to prepare a solution.
  • Example 2 Hydrogenated nitrile rubber (HNBR: trade name “Terban 5065” [k: 33.3, l: 63, m: 3.7, R1 to R5: H]) manufactured by LANXESS was used as a material for the protective layer. Except for this point, the second embodiment is the same as the first embodiment.
  • HNBR trade name “Terban 5065” [k: 33.3, l: 63, m: 3.7, R1 to R5: H]
  • Example 3 Hydrogenated nitrile rubber (HNBR: trade name “Terban 4367” [k: 27.4, l: 69.1, m: 3.5, R1 to R5: H]) manufactured by LANXESS as a material used for the protective layer Except for the points used, the second embodiment is the same as the first embodiment.
  • HNBR trade name “Terban 4367” [k: 27.4, l: 69.1, m: 3.5, R1 to R5: H]
  • Example 4 As a material used for the protective layer, a fully hydrogenated nitrile rubber (NBM: trade name “Terban 3407” [k: 20.5, l: 79.5, m: 0, R1 to R3: H] manufactured by LANXESS) is used. Except for this point, the second embodiment is the same as the first embodiment.
  • NBM fully hydrogenated nitrile rubber
  • Example 5 As a material used for the protective layer, hydrogenated nitrile rubber (HNBR: trade name “Terban 3496” manufactured by LANXESS Co., Ltd. [k: 20.5, l: 68.7, m: 10.8, R1 to R5: H]) Except for the points used, the second embodiment is the same as the first embodiment.
  • HNBR trade name “Terban 3496” manufactured by LANXESS Co., Ltd. [k: 20.5, l: 68.7, m: 10.8, R1 to R5: H]
  • Example 6 Other than the use of acrylonitrile butadiene rubber (NBR: JSR N22L [k: 27.4, l: 36.3, m: 36.3, R1, R4, R5: H]) as the material used for the protective layer Is the same as in Example 1.
  • NBR acrylonitrile butadiene rubber
  • Example 1 is the same as Example 1 except that the integrated irradiation dose of the electron beam is 100 kGy.
  • Example 2 is the same as Example 2 except that no electron beam irradiation was performed.
  • Example 5 is the same as Example 5 except that no electron beam irradiation was performed.
  • Examples 1 to 7 it can be seen that the vertical emissivity is 0.11 to 0.15 (0.20 or less), and the far-infrared reflection characteristics are excellent.
  • the indentation hardness is 1.2 MPa or more, and deformation due to indentation is small.
  • Comparative Examples 1 and 2 are greatly deformed by pressing. Therefore, it can be seen that in Examples 1 to 7, the deformation due to the pressing is greatly suppressed.
  • Example 8 and Example 9 After forming a reflective layer in the same manner as in Examples 1 to 7, a urethane-based adhesive layer was formed on the reflective layer by the following procedure. More specifically, an aqueous urethane resin having a carboxyl group “Superflex 210” (Daiichi Kogyo Seiyaku Co., Ltd.) is applied on the reflective layer, dried at 100 ° C. for 4 minutes, and urethane having a thickness of 100 nm. A system adhesive layer was formed. And the protective layer 3 was formed by the coating method on the urethane type adhesive bond layer.
  • an aqueous urethane resin having a carboxyl group “Superflex 210” (Daiichi Kogyo Seiyaku Co., Ltd.) is applied on the reflective layer, dried at 100 ° C. for 4 minutes, and urethane having a thickness of 100 nm.
  • a system adhesive layer was formed.
  • the protective layer 3 was formed by the coating method on the ure
  • Example 8 the indentation hardness and vertical emissivity of the protective layer 3 were measured in the same procedure as in Examples 1 to 7. Furthermore, the Gakushoku abrasion test was conducted for each of Example 8 and Example 9. More specifically, using a Gakushin dyeing frictional fastness tester (manufactured by Yasuda Seiki Seisakusyo Co., Ltd.), cotton cloth (Kanakin No. 3) was used as the rubbing means, and the specimen (Example 7, A test is performed in which the friction means is brought into contact with 8) and reciprocated 100 times while applying a load of 500 g. The case where the protective layer was not peeled off or very small was evaluated as ⁇ , and the case where the protective layer was peeled over the entire surface and the reflective layer was exposed was evaluated as x.
  • Example 2 is the same as Example 2 except that a urethane-based adhesive layer is formed between the reflective layer and the protective layer.
  • Example 5 is the same as Example 5 except that a urethane-based adhesive layer is formed between the reflective layer and the protective layer.
  • Examples 8 and 9 it can be seen that the vertical emissivity is 0.11 to 0.12 (0.20 or less), and the far-infrared reflection characteristics are excellent.
  • the indentation hardness is 1.2 MPa or more, and deformation due to indentation is small. Therefore, in Examples 8 and 9, it can be seen that the deformation due to the pressing is greatly suppressed.
  • the infrared reflective film which concerns on this invention is not limited to the said embodiment, A various change is possible in the range which does not deviate from the summary of this invention.
  • the polymer composed of at least any two or more of the repeating units A, B, and C has been described.
  • the present invention is not limited to this.
  • Other repeating units other than these repeating units can also be included as long as the properties required for the protective layer are not impaired.
  • Other repeating units include, for example, styrene, ⁇ -methylstyrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, vinyl acetate, (meth) acrylamide Etc.
  • the ratio of these to the whole polymer is preferably 10% by weight or less.
  • the reflective layer 2 is formed by vapor deposition.
  • the present invention is not limited to this.
  • a reflective layer may be prepared separately from the base material by using a reflective film, and the reflective layer may be formed by sticking the reflective film to the base material.
  • the infrared reflective film according to the above embodiment is an infrared reflective film having both heat shielding properties and heat insulating properties.
  • the present invention is not limited to this. Needless to say, the infrared reflective film according to the present invention can also be applied to an infrared reflective film having only a conventional heat shielding property.

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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Selon cette invention, une couche réfléchissante et une couche protectrice sont stratifiées dans l'ordre sur une surface d'un film réfléchissant dans l'infrarouge. Ladite couche de protection contient un polymère contenant lui-même au moins deux unités de répétition parmi les unités de répétition A, B et C dans la formule chimique (I). Cette couche de protection possède une dureté par pénétration d'au moins 1,2 MPa (R1 : H ou un groupe méthyle, R2 à R5 : H, un groupe alcényle ou un groupe alkyle dont le nombre d'atomes de carbone va de 1 à 4).
PCT/JP2012/082351 2011-12-16 2012-12-13 Film réfléchissant dans l'infrarouge WO2013089187A1 (fr)

Priority Applications (3)

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EP12856615.5A EP2792484A1 (fr) 2011-12-16 2012-12-13 Film réfléchissant dans l'infrarouge
US14/365,258 US20140327959A1 (en) 2011-12-16 2012-12-13 Infrared reflective film
CN201280062240.3A CN103987522A (zh) 2011-12-16 2012-12-13 红外线反射薄膜

Applications Claiming Priority (4)

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JP2011276331 2011-12-16
JP2011-276331 2011-12-16
JP2012132283A JP2013144427A (ja) 2011-12-16 2012-06-11 赤外線反射フィルム
JP2012-132283 2012-06-11

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CN112708106B (zh) * 2019-10-24 2023-05-02 旭化成株式会社 多异氰酸酯组合物、涂覆组合物和涂覆基材
CN114527608A (zh) * 2020-11-23 2022-05-24 合肥京东方显示技术有限公司 调光面板、其制作方法、其驱动方法及调光建筑玻璃

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JPS55149909A (en) * 1979-05-10 1980-11-21 Teijin Ltd Selective light transmissible laminate
JPS6151762B2 (fr) 1979-05-10 1986-11-10 Teijin Ltd
JPH08501993A (ja) * 1992-10-07 1996-03-05 ザ グッドイヤー タイヤ アンド ラバー カンパニー 保護被覆を有するゴム製品
JP2005195357A (ja) 2003-12-26 2005-07-21 National Institute Of Advanced Industrial & Technology 光学式圧子接触面のその場定量に基づく力学特性計測法及びその試験装置
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EP2792484A1 (fr) 2014-10-22
US20140327959A1 (en) 2014-11-06
CN103987522A (zh) 2014-08-13
JP2013144427A (ja) 2013-07-25

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